Quaternized fluorindine compounds and textile materials dyed therewith



United States Patent O 3,390,948 QUATERNIZED FLUORINDINE COMPOUNDS AND TEXTILE MATERIALS DYED THEREWITH James M. Str'aley and Raymond C. Harris, Kingsport,

Tenn., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Oct. 20, 1965, Ser. No. 499,079 22 Claims. (Cl. 8-55) ABSTRACT OF THE DISCLOSURE Quaternary salts of fluorindine compounds are useful as dyes for acrylic and modacrylic textile materials.

This invention relates to quaternary salts of compounds of the fluorindine series and their use particularly as dyes for acrylic polymer textile materials.

The compounds are quaternary salts of fiuorindines having the general formula wherein the R groups are the same or different and each represents lower alkyl or substituted lower alkyl and X and Y are the same or different and each represents an ortho-phenylene group, a 1,2-naphthylene group, or a 2,3- naphthylene group.

The quaternary salts are prepared by quaternizing the above fluorindines so as to obtain either mono-quaternary or di-qu'aternary salts of the formulas i t a, R

t N N63 X Y 22 i t R; R

in which each R represents lower alkyl or benzyl, R, X and Y are as defined above, and Z represents an anion derived from qu-aternization, e.g. C1 Br CH S 3,390,948 Patented July 2, 1968 sulfonate, ethyl p-toluene sulfonate, n-propyl p-toluene sulfonate and n-butyl p-toluene sulfonate.

The following are representative fluorindines which are quaternized to obtain the quaternary salts of the invention: fluorindine, 5,12-dimethylfiuorindine, 5,12-diethylfluorindine, 5,12 diisopropylfiuorindine, 2,5,9,12 tetram'ethylfluorindine, 3,10-bis(trifiuoromethyl)-5,12-dimethylfluorindine, 2,9-dibromo-5,12-dimethylfluorindine, 2,9- dinitro 5,12 dimethylfluorindine, 5,l2-di(B-cyanoethyl) fluorindine, 5,12-di(fi-hydroxyethyl)fluorindine, 5,12-dibutylfiuon'ndine, 2,5-dimethyl-l2-ethylfiuorindine, 2,5-dimethylfluorindine, 12-ethylfluorindine, 2,9-'bis(sulfonamido)-5,12-diethylfiuorindine, 2,9-dimethoxy-5,12 diethylfluorindine, 5,12-dimethyl-dibenzo[b,rn]fluorindine.

Fluorindine, itself,

is a known compound as is 5,12-diphenylfluorindine. The other fluorindines substituted in at least the 5,12-positions are prepared by reaction of 2,5-dihydroxy-1,4-benzoquinones with the appropriate o-phenylenediamine or o-naphthalenediamine in the presence of pyridine or an alkylpyridine as described in our co-filed US. patent application Ser. No. 499,078 and illustrated in the examples below. In that application the above compounds are named primarily as 5,12 lihydroquinoxal0[2,3-b]phenazines. The unsymmetrical fluorindines described above Where the R groups are different are prepared as described in our above patent application by reaction of a hydroxyphenazinone as illustrated in the examples below.

The quaternized fluorindine compounds are especially useful as dyes for acrylic polymer textile materials such as those containing acrylonitrile units yielding blue and green dyeings having good fastness, for example to light, washing, perspiration, gas (atmospheric fumes), and sublimation. The fiuorindines can also be expected to respond favorably to other tests as textile dyes when tested by methods such as described in the A.A.T.C.C. Technical Manual, 1964 Edition. The degree of utility varies, for example, depending upon the textile material being dyed and the formula of the particular fluorindine in use. Thus, all of the quaternary fluorindine compounds will not have the same degree of utility for the same textile material. The described quaternary fluorindine compounds generally have better light-fastness and wet-fastness properties than do the corresponding non-quaternary flnorindines. They can be expected to show less cross-staining when dyeing mixtures of acrylic fibers with other fibers.

As can be seen from the following examples, the substituents attached to the alkyl or aryl groups R of the above formula, and to the ortho-phenylene groups represented by X and Y can be varied widely and function primarily as auxochrome groups to control the color of the fluorindine compound. Accordingly, the substituted alkyl groups represented by R includes hydroxyal'kyl, e.g. hydroxyethyl, polyhydroxyalkyl, e.g. 2,3-dihydroxypropyl; alkoxyalkyl, e.g. methoxyethyl; cyanoalkyl, e.g. B- cyanoethyl; cyanoal-koxyalkyl, e.g. fi-cyanoethoxyethyl, acyloxyalkyl, e.g. acetoxyethyl; carboalkoxyalkyl, e.g. carbethoxyet-hyl; halogenoalkyl, e.-g. chloroethyl; hydroxyhalogenoalkyl, e.g. 8-hydroxyy-chloropropyl; alkylsulfonylalkyl, e.g. methylsulfonylethyl;

N-methylsulfonamidoethyl; sulfonamido, alkylsulfonamido e.g. N-methyl sulfonamido; alkylcarbonamidoalkyl, e.g. ethylcarbonamidocthyl; dicarboxamidoalkyl, e.g. ,B-dicarboxamidoethyl, etc. Substituents on the ortho phenylene groups represented by X and Y include alkyl e.g. methyl, alkoxy e.g. methoxy, nitro, amino, cyano, halogen, alkylsu'lfonyl e.g. methylsulfonyl, alkylsulfonamido e.g. methylsulfonamido, alkanoylamido e.g. acetamido, alkylthio e.g. methylthio, carbamoyl, etc. The compounds where R is alkyl or substituted alkyl may have better affinity than compounds where R is an aryl group such as phenyl.

The following example illustrates one way in which the fluorindine compounds of the invention can be used to dye acrylonitrile polymer textile material. .1 gram of dye is dissolved by warming in cc. of methyl Cellosolve. A 2% aqueous solution of a non-ionic surfactant, such as Igepal CA (a polymerized ethylene oxide-alkylphenol condensation product), is added slowly until a fine emulsion is obtained and then the dye mixture i brought to a volume of 200 cc. with warm water. 5 cc. of a 5% aqueous solution of formic acid or acetic acid are added and then grams of fabric made from an acrylic fiber is entered and in the case of Orlon 42 the dyeing is carried out at the boil for one hour. In the case of materials made of Verel acrylic fiber the dyebath temperature should not exceed 90 C. in order to avoid damage to the fiber. The dyed material is then washed well with water and dried.

Representative acrylonitrile homopolymer and copolymer textile materials dyed by the fiuorindine compounds, especially the above 5,12-alkyl and substituted alkyl fluorindines, are characterized by containing at least about 35% combined acrylonitrile units and up to about 95% acrylonitrile units, and modified, for example, by 85-5 of vinyl pyridine units as described in US. Patents 2,990,- 393 (Re. 25,533) and 3,014,008 (Re. 25,539) or modified by 65-5% of vinylpyrrolidone units, for example, as described by US. Patent 2,970,783, or modified with 65-5 acrylic ester or acrylamide units as described in US. Patents 2,879,253, 2,879,254 and 2,838,470. Similar amounts of the other polymeric modifiers mentioned above are also useful. A preferred group of the copolymers readily dyeable with the fiuorindines are the modacrylic polymers such as described in US. Patent 2,831,- 826, composed of a mixture of (A) 70-95% by Weight of a copolymer of from to 60% by weight of vinylidene chloride or vinyl chloride and 70-35% by weight of acrylonitrile, and (B) 305% by weight of second polymer from the group consisting of (1) homopolymers of acrylamidic monomers of the formula wherein R is selected from the group consisting of hydrogen and methyl, and R and R are selected from the group consisting of hydrogen and alkyl groups of 1-6 carbon atoms, (2) copolymers consisting of at least two of said acrylamidic monomers, and (3) cop'olymers consisting of at least 50% by weight of at least one of said acrylamidic monomers and not more than 50% by weight of a polymerizable monovinyl pyridine monomer.

A particularly efficacious group of modacrylic polymers is an acetone soluble mixture of (A) 70-95% by weight of a copolymer of 30-65% by weight of vinylidene chloride and 70-35% by weight of acrylonitrile and (B) 30-5 by weight of an acrylamide homopoiymer having the above formula wherein R R and R are as described above. Specific polymers of that group contain 70-95% by weight of (A) a copolymer of from 30-65% by weight of vinylidene chloride and 70-35% by weight of acrylonitrile and (B) 30-5% by weight of a lower N-alkylacrylamide polymer such as poly-N-methacrylamide,

4 poly-N-isopropylacrylamide and poly-N-tertiarybutylacrylamide.

The following examples will serve to illustrate the synthesis and use of the fiuorindine compounds.

EXAMPLE 1.-5, l2 DIHYDRO 5,12 DIMETHYL- QUINOXALO [2,3 -b] PHENAZINE(5,12 DIMETH- YLFLUORINDINE) precipitate was washed with hot water, then with acetone and air-dried. The product was a dark powder, soluble in methanol and dilute mineral acids with a clear blue color. The acid solutions give a typical ruby-red fluorescence in ultraviolet light.

Q uaternization A slurry of 5 g. of 5,lZ-dihydro-S,lZ-dimethylquinoxalo[2,3-b]phenazine in 25 ml. of dimethylsulfate was stirred for 8 hours at 25 C. The reaction mixture was then added slowly to 500 ml. of water at 50 C. The temperature was raised to C. and the solution stirred for /2 hour at 95 C. Twenty-five grams of sodium iodide was then added. The mixture was chilled and filtered. The precipitate was washed with water and dried at 60 C. The quaternary iodide thus formed dyed acrylic fibers in bright blue shades with excellent fastness properties. The dye gives a slightly greener shade than the unquaternized material.

EXAMPLE 2.-5,12-DIETHYL-5, IZ-DIHYDRO- QUINOXALO [2,3-b] PHENAZINE 18 g. N-ethyl-o-phenylenediamine dihydrochloride and 5.6 g. of 2,5-dihydroxy-1,4-benzoquinone in 75 ml. of pyridine were refluxed, with good agitation for 24 hours. The reaction mixture was then cooled and filtered. The precipitate was washed with warm water until the filtrate came through a clear blue. It was then washed with acetone and air-dried. Yield15 g. of a black crystalline powder which gave a bright blue solution in dilute mineral acids and methanol.

Quaternization Five grams of 5,12-dihydro 5,12 diethylquinoxalo- [2,3-b]phenazine in 25 ml. of dimethylsulfate was stirred seven hours at 25 C. The reaction mixture was drowned in 500 ml. of ethyl acetate. The mixture was filtered and the precipitate thoroughly washed with ethyl acetate and dried at 60 C. The methosulfate quaternary salt dyed acrylic fibers bright fast blue shades. 6.8 g. (.02 mole) 5,12-dihydro-5,l2-diethylquinoxalo[2,3-b1phenazine in 25 ml. of diethylsulfate was stirred for five hours at 25 C. The reaction mixture was poured into 700 ml. of water and the temperature raised to 95 C. The solution was stirred /2 hour at 95 C. and filtered hot. Twenty grams of sodium iodide was added and the reaction mixture was cooled and filtered. The precipitate was recrystallized from water. The resulting 5,l2-dihydro-5,5,l2-triethyl quinoxalo[2,3-b]phenazinium iodide dyes acrylic fibers in fast blue shades. The quaternary salt has the formula:

FLUORINDINE 4.8 g. of l0-ethyl-3-hydroxy-2-phenazinone and 4 g. of l-N-4-dimethyl-o-phenylenediamine dihydrochloride are added to 25 g. of 3-picoline. The reaction mixture is Quaternization 4.77 g. of the above trialkylfiuorindine'in 80 ml. of dry toluene is heated to 90 C. and 6.66 g. of dimethylsulfate is added over a period of 15 minutes. The temperature is kept at 8590 C. during the addition and for 15 minutes thereafter. A mixture of 25 m1. of isopropanol and 3 ml. of water is then added slowly and the reaction mixture refluxed for 15 minutes, chilled to 5-10 C. and filtered. The filter cake was washed with cold toluene and dried at 60 C. Yield is 6.5 g. (99.5% The quaternary dyes acrylic fibers in bright, blue shades with excellent fastness properties.

The compound has the formula Quaternization EXAMPLE 4.5 IZ-DIMETHYL-DIBENZO [b,m] FLUORINDINE Forty-nine grams of 2-amino-3-methylaminonaphthalene dihydrochloride and 14 g. of 2,5-dihydroxybenzoquinone in 150 ml. of 3-picoline were refluxed with stirring for 3 hours. The reaction mixture was then cooled and filtered and the product thoroughlywashed with 6. warm water. The precipitate was then washed with 3% sodium hydroxide until the filtrate came through colorless. It was then washed with water until alkali-free and dried at 60 C. The material dyes acrylic fibers fast blue shades. Quaternization with dimethylsulfate gave a product which dyes acrylic and modacrylic fibers in fast, blue shades.

Additional fiuorindine compounds shown in the following tables, prepared as described in our above patent application, are quaternized in the manner described in the above examples and yield mono-quaternary or di-quaternary fiuorindine compounds which dye acrylonitrile polymer fibers to blue shades of good fastness properties.

The compounds of this table are symmetrical compounds of the formula:

Il a R2- N\ %I\.I\ R1 R1 y R1 1i. TABLE Example:

-SOzCH3 -H C2 a H -o,H, s -C:Hs -CH C2H5 -H C3H5 CH3 11 -C1 -H CH CH /CH; 12 -H -CF CH CH 13 -SO2NH2 -H C{I 14 -SO2NHCH3 'H C4Ho 15 -C1 -C1 C Hp 16 -SO2NH2 -H -G4Ho The compounds of this table are unsymmetrical compounds of the formula:

R4 i N R1 TABLE R4 R5 R0 R1 R5 Color on Orlon Example 17 -C2H5 -CH3 H H H Blue. 18 --CzH5 CHa H Z-CH; H D0.

CH3 19 -C:H5 -C& H H H D0.

CH H 2-NO2 H Reddish blue.

CHiCHaOH H H H Blue.

- H H 2-SOzCH H Reddish blue.

CH3 H 1,2- Blue.

TABLECon tinned R4 R5 R6 R1 Ra Color on Orlon 27 C1H -CH H 2.3- Do.

28 CII C H CH; H: H Do.

/0 H; 29 CH; CH Q-SOzNHz H H Reddish blue.

30 -CH -C2H Q-CFa H H D0.

/0 H3 31 CH CH; H Z-SOzCH: H De.

CH 32 -05 -CII; H 2-NO: H D0.

C Hi

0 H 33 CH C2Ha 9-01: H H Do.

/C H; 34 CH CHCH;OH H H H Blue.

/C H; CH; 35 CH --CIIzCII:CHzN-CH3 H H H Do;

C Ha 36 CH C4Hv n H H H Do.

37 -CtHg -CH3 H H H D0. 38 C4Hg CHzCHzOH H H H D0.

(3H C HnCHzCHzN-C H; H H H D0.

CI-I; H 2'SQ2N H: H D0. -C H H Z-CF; H Reddish blue. CH H 3-SO CH H Blue. H3 1 Z-NO, H Reddish blue. -CH U-SOzNHg 2-CH H D0. C1 3 9-SO2NH 2-NO: H Red blue. CH Q-SOzNHz 2-CF3 H D0. CII2CH1CH7N(CH3) Q-SOgNHg II II Blue. -C H H Q-CF; H Reddish blue: CgH H H H Blue. C]'I I1]: Z-N Hg H DO. CH H Z-OHC; H Green blue. CH H 2-0 CH H Blue. /CH; 53 -CHCH;CH;N -CH3 H 2-CH H D0.

54 CgH5 CH: H Z-NH: 3-Cl D0. 55 CQI{5 CII1 II Z-OCH; 3Cl Dr The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereina'bove, and as defined in the appended claims.

What we claim is:

1. A compound having the formula 2. A compound having the formula T] N N x Y Z [in]... I i

wherein X and Y are the same or difierent and each represents ortho-phenylene; ortho-phenylene substituted with lower alkyl, trifluoromethyl; halogen, hydroxy, lower alkylsulfonyl, sulfamoyl, or nitro; 1,2-naphthylene; or 2,3-

naphthylene;

R represents lower alkyl; R represents lower alkyl;

m and n each represent 0 or 1, the sum of m and n being 1; and

Z represents an anion 3. A compound according to claim 2 wherein X and Y each represents ortho-phenylene or orthophenylene substituted with lower alkyl; R represents methyl or ethyl; and Z represents CH SO or C H SO 4. A compound having the formula wherein Z is an anion.

5. A compound having the formula wherein Z is an anion.

6. A compound having the formula wherein Z is an anion.

l 0 9. A compound having the formula SOzNH,

HINSO \N N wherein Z is an anion.

10. A compound having the formula l /N\ ZN\ OCH,

l (1H3 02H;

wherein Z is an anion.

11. .A compound having the formula (|JH(CH3)2 f e a (EH3 a):

wherein Z is an anion.

12. A compound having the formula wherein Z is an anion.

13. A compound having the formula l N N [I f j USWNHI Z9 N N 31H: (3H3 wherein Z is an anion.

14. A compound having the formula wherein Z is an anion.

15. A compound having the formula r N a Ha hHo wherein Z is an anion.

16. A compound having the formula wherein Z is an anion.

17. A compound having the formula CzH5 wherein Z is an anion.

18. A compound having the formula CH3 CH3 wherein Z is an anion.

1 2. 19. A compound having the formula llzHs 5 omsoi 15 compound of claim 3.

No references cited.

HENRY R. JILES, Primary Examiner. 

